Nematocidal agents



United States Patent Office 32,203,852 Patented Aug. 31, 1965 3,203,852NEMATOCIDAL AGENTS Horst Werres, Berlin-Charlottenhurg, and ErnstAlbrecht Pieroh, Berlin-Hermsdorf, Germany, assignors to Schering, A.G.,Berlin, Germany No Drawing. Filed Nov. 21,1961, Ser. No. 154,020 Claimspriority, application Germany, Nov. 30, 1%0, Sch 28,860 24 'Claims. (Cl.167-22) wherein R is a radical selected from the group consisting oflower alkyl, monohalogenphenyl and radicals of the formula and R is aradical selected from the group consisting of lower alkyl, phenylradicals, and radicals or" the formula wherein n is an integer between 1and 4.

The compounds are prepared in a manner known per se by reacting thecorresponding chlorides of the carboxylic acids with dithiocarbamatesalts. The following example illustrates the preferred method forpreparing the mixed anhydrides of the invention.

(1) The mixed anhydride of adipic acid and N-propyldithiocarbarnic acidMelting point between 7779 C.

(2) The mixed anhydride of suberic acid and N- bromophenyldithiocarbamicacid Melting point between 105106 C. (decomposes).

(3) The mixed anhydride of sebacic acid and N- propyldithiocarbamic acidMelting point between 7879 C.

(4) The mixed anhydride of sebacic acid andN-pbromophenyl-dithiocarbamic acid Melting point 106-109 C.(decomposes).

(5) The mixed anhydride of acetic acid and N-pbromophenyl-dithiocarbamicacid Melting point between 88-90 C. (decomposes).

(6) The mixed anhydride of benzoic acid andN-pchlorophenyl-dithiocarbarnic acid Melting point between 79-80 C.

(7) The mixed anhydride of p-nitro-benzoic acid andethylene-bis-dithiocarbamic acid EXAMPLE 1 19.4 g. (0.1 mole) ammoniumN-isopropyl-dithiocarbamate are suspended in 150 ml. ethyl ether and11.95

Melting point between 108108.5 C. (decomposes).

(8) The mixed anhydride of phenylacetic acid andethylene-bis-dithiocarbamic acid g. (0.05 mole) sebacoyl dichloride areadded drop by Melting point between 103-104 drop over a period of 25minutes with agitation while the reaction mixture is being cooled withice to temperature of 5 to 7 C. Stirring is continued for 15 minutesafter the sebacoyl dichloride has been added. The solid precipitateformed is filtered off with suction, dispersed in water and againfiltered. It is finally dissolved in chloroform and reprecipitated bymeans of petroleum ether.

The mixed anhydride of sebacic acid and N-isopropyL dithiocarbamic acidhaving the formula is obtained in a yield of 14.5 grams. It melts anddecomposes at 90-91" C.

When the corresponding acyl chlorides and dithiocarbamates orethylene-bis-dithiocarbamates are substituted for the afore-rnentionedstarting materials in equimolecular amounts there are obtained thefollowing compounds in an analogous manner:

C. (decomposes). (9) The mixed anhydride of suberic acid andN-pchlorophenyldithiocarbamic acid Q S O O S Solid compound, soluble inCHCI Analysis.-Calculated: C, 48.5%; H, 4.0%; N, 5.1%. Found: C, 48.9%;H, 4.4%; N, 5.2%.

The nematocidal agents of the invention may be employed singly, or inmixtures with each other, with other nematocidal agents, and with otherpesticides. Nematocidal compositions containing the novel compounds areprepared in a manner well known to those skilled in the art by mixingthe active ingredient with adjuvants, carriers, fillers, and the like,which themselves may be without significant nematoeidal activity. Bothsolid and liquid compositions may be prepared as is well known. Suitablesolid carriers include limestone, bentonite, diatomaceous earth, fullersearth, silica, pyrophillite, talcum, gypsum and-like materials in finelycomminuted form.

Such preparations may be prepared for instance by grinding together theactive compound, the solid carrier and an emulsifier, for example 20%active substance 79% of an aluminum silicate carrier substance 1% of ansurface active agent on basis of salts of sulfurized amides of higherfatty acids Preparations of this type may be applied directly bystrewing into the nematode-infested soil or by dispersing in water andspraying.

The active substance may also be dissolved in any suitable solvent andafter adding an emulsifier the solution emulsified in water.

There are many modifications of these preparations possible. The portionof the active compound may vary between about 1 to 99 percent as it isdesired for special purposes and there may be added further compounds.

The nematocidal agents of the invention are compatible with emulsifiers,wetting agents, binders, propellent gases, perfumes, and stabilizersconventionally employed in this art for preparing liquid concentrates orspray mixes in aqueous or other media. The liquid compositions may bepropelled by mechanical pumps or by the pressure of compressed gases toform coarse droplets or aerosols.

ematocidal effects typical of those capable of being achieved with thenematocidal agents of our invention are set forth in Example 2, but itwill be understood that all compounds of the invention have similareffects on the nematodes specifically mentioned in the followingexample, and on others.

EXAMPLE 2 Nematode larvae are freshly collected from plant parts and arethen dispersed in 2 ml. of an aqueous suspension or aqueous emulsion ofa solution of the active agent in acetone. After hours standing at C.,the live and dead larvae are counted in each specimen. The nem atodesemployed in these tests are Ditylenclzus dipsaci (Kiihn Filipjev) (codeletter D) Aplzelenchoides ritzemab'osi [(Schwartz) Steiner] (code letterA) Meloidogyne ilzcognita [(Kofoid & White) Chitwood] (code letter M)The results of the count are expressed in the following table inpercentage of dead larvae among all larvae counted in a specimen. Sixnematocidal agents of the invention are tested at four differentconcentrations against larvae of the above three nematodes.

Table Concentration of agent in percent Active agent Code letterAnhydride of acetic and N- D 100 100 100 100 p-bromophenyl-dithiocar- {A100 100 100 100 bamic acids. M 100 100 100 100 Anhydride of suberic acidD 100 100 100 50 an N-pbromophenyl-di- A 100 100 100 98 thiocarbamicacid. M 100 100 100 100 Anhydride of benzoic acid D 100 100 100 50 andN-p-chlorophenyl- {A 100 100 100 100 dithiocarbamic acid. M 100 100 100100 Anhydride of sebacic acid D 100 100 98 0 and 0t N-p-bromophenyl- A100 100 100 100 dithiocarbamic acid. M 100 100 100 Anhydride of adipicacid D 98 0 0 and N-propyl-dithiocar- A 90 0 O bamic acid. M 100 100 0Anhydride of sebacic acid D 70 5O 3O 0 and of N-propyl-dithio- A 80 30 00 carbamic acid. M 100 70 70 O Anhydride of p-nitro-ben- D 100 100 80 50zoic acid and ethyleuc bis A 100 100 100 100 dithio-carbamic acid. M 100100 100 100 Anhydride of phenyl-acetic D 100 100 80 acid andethylene-bis- A 100 100 100 dithiocarbamic acid. M 100 100 100 100Obviously many modifications and variations of the present invention arepossible in the light of the above teachings. It is therefore to beunderstood that within the scope of the apepnded claims, the inventionmay also be practiced otherwise than as specifically described.

We claim:

1. A nematocidal composition containing a carrier free of significantnematocidal activity, and further containing as the active ingredientthereof in a nematocidally effective amount, a compound of the formulawherein R is selected from the group consisting of lower alkyl,monohalogen-phenyl, nitrophenyl, and

and R is selected from the group consisting of lower alkyl, phenyl,nitrophenyl, and

wherein n is an integer between 1 and 4.

2. A composition as set forth in claim 1, wherein said compound is themixed anhydride of adipic acid and N-propyl dithiocarbamic acid havingthe formula 3. A composition as set forth in claim 1, wherein saidcompound is the mixed anhydride of suberic acid and N-pbromophenyl-dithiocarbamic acid having the formula 4. A composition asset forth in claim 1, wherein said compound is the mixed anhydride ofsebacic acid and of N-propyl-dithiocarbamic acid having the formula 5. Acomposition as set forth in claim 1, wherein said compound is the mixedanhydride of sebacic acid and of N-isopropyl-dithiocarbamic acid havingthe formula 6. A composition as set forth in claim 1, wherein saidcompound is the mixed anhydride of sebacic acid and ofN-p-bromophenyl-dithiocarbamic acid having the formula 7. A compositionas set forth in claim 1, wherein said compound is the mixed anhydride ofacetic acid and N-pbromophenyl-dithiocarbamic acid having the formula 8.A composition as set forth in claim 1, wherein said compound is themixed anhydride of benzoic acid and N-p-chlorophenyl-dithiocarbamic acidhaving the formula 9. A composition as set forth in claim 1, whereinsaid compound is the mixed anhydride of ethylene=bis-dithiocompound isthe mixed anhydride of sebacic acid and of carbamic acid and p-nitrobenzoic acid having the formula N-propyl-dithiocarbamic acid having theformula 10. A composition as set forth in claim 1, wherein said compoundis the mixed anhydride of phenyl acetic C H NHCSSCO(CH acid andethylene-bis-dithiocarbamic acid having the CO+CSNH-C H formula 0 S ISI0 0112-93-Si JNHCH2CHzNHCSi J-CH2 11. A method of killing nematodeswhich comprises 16. A method as set forth in claim 12, wherein saidexposing said nematodes to a nematocidal amount of a compound is themixed anhydride of sebacic acid and of compound of the formulaN-isopropyl-dithiocarbamic acid having the formula RNH-CS-S--COR' 3 72)a COS-CSNHC H wherein R is selected from the group consisting of loweru alkyl, monohalogen-phenyl, and 17. A method as set forth in cla1m 12,wherein said CH compound is the mixed anhydride of sebacic acid and ofN-p-bromophenyl-dithiocarbamic acid having the formula and R is selectedfrom the group consisting of lower BICGH4 NH CS S CO (CH2)8alkyl,phenyl, and S (CH2)21 cO s CS NH R 18. A method as set forth inclaim 12, wherein said whereinnisaninteger betweenland 4. compound isthe mixed anhydride of acetic acid and 12. A method of killing nematodeswhich comprises N-p-bromophenyl-dithiocarbamic acid having the formulaapplying to nematode infested soil a nematocidal amount 3 f d f theformula 0 acompoun o O 19. A method as set forth in claim 12, whereinsaid RNH CS S C compound is the mixed anhydride of benzoic acid andwherein R is selected from the group consisting of lowerN-p-chlorophenyl-dithiocarbamic acid having the formula alkyl,monohalogen-phenyl and C1C H NHCSS-CO-C H CHZCHZ NH CS S CO R' 20. Amethod as set forth in claim 12, wherein said and R is a radicalselected from the group consisting compound is the mixed anhydride ofethylene-bis-dithio- 40 carbamic acid and p-nitro-benzoic acid havingthe formula 0 s s o oat-Q-b-s-ii-Nm-om-onrNH-iLs-ii-QN o,

21. A method as set forth in claim 12, wherein said compound is themixed anhydride of phenyl acetic acid and ethylene-bis-dithiocarbamicacid having the formula C t S O -oH2o-s-bNH-omoHzNH- i-s-iLom-Q of loweralkyl, phenyl, and radicals of the formula 22. A method of killingnematodes which comprises applying to nematode infested soil anematocidal amount (CHZ)ZH CO S CS NH R of a compound of the formulawherein n is an integer between 1 and 4.

13. A method as set forth in claim 12, wherein said R1 NH* CS S CO(CH2)2111 compound is the mixed anhydride of adipic acid and r CO S CSNH R2 N-propyl-dithiocarbamic acid having the formula wherein R and Rare members of the group consisting C H NH C O (CHzh of lower alkyl andmonohalophenyl, and m is an integer between 2 and 4. CO CSNH C3H7 23. Amethod of killing nematodes which comprises 14. A method as set forth inclaim 12, wherein said applying to nematode infested soil a nematocidalamount compound is the mixed anhydride of suberic acid and of acompoundof the formula N-p-bromophenyl-dithiocarbamic acid having the formula SCO R4 BI C6H4 NH CS S %E H Br wherein R and R are members of the groupconsisting S C 6 4 of lower alkyl, phenyl, and monohalophenyl. 15. Amethod as set forth in claim 12, wherein said 24. A method of killingnematodes which comprises applying to nematode infested soil anematocidal amount of a compound of the formula wherein R and R aremembers of the group consisting 5 of phenyl-(lower) alkyl tndnitrophenyl.

References Cited by the Examiner UNITED STATES PATENTS Searle 260-545Harman 16722 Scott et a1. 260545 Luckenbaugh 16713 Pieroh et a1. 16722Heusch et a1 16722 Beaver et a1. 16713 Werres et a1 16722 0 JULIAN S.LEVITT, Primary Examiner.

CHARLES B. PARKER, Examiner.

1. A NEMATOCIDAL COMPOSITION CONTAINING A CARRIER FREE OF SIGNIFICANTNEMATOCIDAL ACTIVITY, AND FURTHER CONTAINING AS THE ACTIVE INGREDIENTTHEREOF IN A NEMATOCIDALLY EFFECTIVE AMOUNT, A COMPOUND OF THE FORMULA